In this paper, we report on the electrophoretic deposition and characterisation of pure sodium alginate coatings on titanium biomaterials, the commercially pure titanium CP-Ti1 and Ti–13Nb–13Zr titanium alloy. Various solutions differing in the distilled water to ethanol volume ratio and sodium alginate concentration were used for coating deposition. Uniform, dense and continuous coatings with a thickness up to 1 µm were deposited. The effect of surface topography and morphology, wettability and surface free energy as well as surface chemistry on the coating adhesion to the titanium biomaterials were investigated. The coatings exhibited very good adhesion to the polished and then chemically treated alloy. The adhesion mechanisms were identified. The chemical bonding and interfacial adhesion mechanisms are plausible. The coatings exhibited low surface development, dependent on the applied substrate roughness. Sodium alginate coatings on both substrates showed moderate hydrophilicity and relatively high surface free energy, on average 30 pct higher in comparison with that of the substrate materials. The obtained results will be useful for the further development of composite sodium alginate coatings for enhancing the biological performance of titanium biomaterials.